Scale inhibiting compositions



,llnited States Patent 3,502,587 SCALE INHIBITING COMPOSITIONS James R. Stanford and Paul G. Vogelsang, Jr., Houston, Tex., assignors t0 Nalco Chemical Company, Chicago, Ill., a corporation of Delaware No Drawing. Filed Oct. 6, 1966, Ser. No. 584,672 Int. Cl. C23f 14/02 US. Cl. 252-180 15 Claims ABSTRACT OF THE DISCLOSURE At least partially water soluble 'phosphated mixed esters of polyols containing at least one hydroxyethyl group and 'monhydric surface active compounds containing oxyethylene groups are added to water containing scale forming chemicals to inhibit scale deposition on solid surfaces, especially in oil wells, waterfloodin-g systems in oil wells, cooling systems, boiler feedwaters, and in the prevention of scale deposits in effluent and disposal waters. The invention is especially useful in squeeze-type operations in oil recovery systems where the chemical must be adsorbed on the underground formation in such a manner that it is slowly released into the water as its passes over the formation.

This invention in general pertains to at lea-st partially water soluble phosphated mixed esters of oxyalkylated polyols and monohydric surface active compounds and to uses thereof as scale inhibitors.

The preferred compositions of "the invention are phosphated mixed esters of (A) either oxyethylated or oxypropylatedaterminally oxyethylated polyols, e.g., polyoxyethylated glycerol, ethylene glycol, hexylene gyool, sorbitol, mannitol or trimethylolpropane, or oxyethylated or oxypropylated-terminally oxyethylated erythritol, arabitol, xylitol, quercitol, inositol, and mono-, di-, or tripen taerythritol and (B) oxyalkylated monohydroxy surface active compounds, e.g. oxyethylated nonyl phenol, oxyethylated tridecyl alcohol, and oxyethylated normal alcohol mixtures containing six or more carbon atoms.

The oxyalkylated :polyols and surface active agents are phosphated by reaction with polyphosphoric acid or phosphorus pentoxide at elevated temperature, preferably in the order of about 50 C.-175 C. The reaction time is preferably at least about 30 minutes. The reaction may be conducted longer, however, e.g., up to 3-5 hours, to assure complete reaction. If desired, a catalyst such as BF etherate complex may be used. When using polyphosphoric acid the oxylated polyol and the oxyalkylated surface active agent can be added to the polyphosphoric acid liquid. Conversely, the polyphosphoric acid can be added to a mixture of said oxylkylated polyol and surface active agent.

The resultant reaction product may be used as is, or it may be converted to a salt by partial to complete neutralization with an alkaline substance such as, for example, potassium or sodium hydroxide, potassium or sodium carbonate, ammonia, or a basic amino compound, e.g., tetramethyl ammonium hydroxide, methylamine, ethylamine, diethylamine, triethanolamine, diethanolamine, triethyl amine, ethylene diamine, 'diethylene tria-mine, pyridine, morpholine or other amine. The amine should preferably be a water soluble amine or at least one that does not destroy solubility in water.

The polyols contain at least one, and preferably an average of at least about two, 2-hydroxyethyl groups (CH CH OH) provided by the oxyethylation. The primary hydroxyl groups thereof are more effective than the secondary hydroxyl groups which would be provided by oxypropylation 2-6 carbon atoms, R is a member selected from the group consisting of -CH CH and x is a number average in the range of 0-5 inclusive, y is a number average in the range of 1-6, inclusive, preferably 3-5, and the sum of x plus y equals 2-6, and z is a number average in the range of 0-30, inclusive, and (B) a monohydric oxyalkylated surface active agent having a terminal 2-hydroxyethyl group, said phosphated composition-s having an ave-rage of at least one and up to all of the hydroxyls of the 2-hydroxy ethyl groups and on an average of zero up to substantially all of said hydroxyl groups directly attached to the radical R replaced by phosphate ester groups derived from said phosphorus pentoxide, or polyphosphoric acid, said phosphate ester groups consisting essentially of one or both of a member selected from the group consisting of Also, the invention embraces the salts derived by the partical to complete neutralization of the phosphate ester groups.

Preferred embodiments include those in which said polyol is derived by oxyethylation of glycerol with 1.5 to 2.5 mols of ethylene oxide per mol of glycerol; those in which said polyol is derived by the oxyethylation of mannitol with about 2-20 mols of ethylene oxide per mol of mannitol; those in which said polyols are derived by the oxyethylation of sorbitol with about 2-20 mols of ethylene oxide per mol of sorbitol; those in which said polyol is derived by the oxyethylation of trimethylolpropane with 1.5 to 2.5 mols of ethylene oxide per mol of trimethylolpropane; those in which said monohydric surface active agent is derived by the oxyethylation of a-lk-yl phenols, e.g., containing 4 to 12 carbon atoms in the alkyl group or groups, preferably nonyl phenol Or dinonyl phenol or mixtures thereof, or primary alcohols containing 6 to 18 carbon atoms, preferably tridecyl alcohol, or mixed 6-10 carbon atoms alcohols, with 2-20, preferably 4-14 moles of ethylene oxide per mole of such monohydric substance.

The invention further embraces a process for prevent ing hardness scale deposits on metal surfaces in contact with hard water containing hardness scale-forming ions which comprises contacting said metal surfaces with said hard water while maintaining therein a hardness-ion-precipitation-preventing quantity in the order of 0.5-100 parts per million of the previously described mixed esters and salts thereof.

The invention is particularly suitable for scale prevention by natural brines on ferrous metal walls and other surfaces in oil producing and water flood systems. In organic polyphosphates have long been the most effective and economical sequestering agents used for the prevention of alkaline deposits in both oil producing and water flood systems. However, due to the problems encountered in feeding inorganic polyphosphates and their incompatibility with many waters, a need for a liquid organic phosphate with good solubility in waters containing hardness ions has become increasingly evident. For this reason, a liquid product with good solubility in produced waters and having the effectiveness and low treating cost of inorganic polyphosphates is needed.

The invention has utility in the prevention of similar scale deposits occuring in closed and once-through cooling systems where hard water is employed.

The compounds may also have utility in boiler feed waters and in waters charged to certain desalinization equipment Where scale deposition is a problem.

The invention may also be used in the prevention of scale deposits in certain efiluent and disposal waters, particularly where other materials used in the prevention of such deposits may constitute a pollution problem.

The following are examples of preferred embodiments of the invention wherein the parts are by weight unless otherwise indicated.

Example I Glycerine and finely ground potassium hydroxide are charged into an oxyalkylation reactor and are heated to 150 C. while purging the reactor with natural gas. Ethylene oxide is added slowly at ISO-160 C. until the weight amount of added ethylene oxide equals the weight of glycerine. The reactor contents are recycled for an additional hour after all the ethylene oxide is added to assure essentially complete oxyalkylation. The weight of the added KOH was about 0.1% of the total weight of glycerinc and ethylene oxide.

The phosphating procedure comprises charging 100 parts of the above polyoxyethylated glycerine, parts oxyethylated nonyl phenol (56.6% nonyl phenol and 44.4% ethylene oxide) and 30 parts of 99% isopropanol, the latter as a viscosity control agent, into a vessel free from moisture and oily or other foreign material. The charge is heated to 50 C., whereupon 200 parts of polyphosphoric acid (also called 115% phosphoric acid) is added in small amounts whereby the exothermic reaction is controlled by the rate of addition and by cooling to maintain a temperature of 90 C. when the polyphosphoric acid has been added, the temperature is allowed to increase to the range of -9S C. for about 30 minutes, or less if the clarity of the reaction mass indicates complete reaction.

With the reactor on full cooling, 350 parts of tap water is added, slowly in the initial phase of water addition.

The product is an aqueous solution of mixed esters and mixtures of esters containing some monophosphate and some di-phosphate. Some of the esters are monomeric and some polymeric. Of course, some phosphated oxyalkylated monohydric surface active agent can be present as well as some phosphated oxyalkylated polyol. While the phosphated surface active agent alone will have some scale inhibitor properties, the phosphated oxyalkylated polyol is more effective, and the combination of the two, especially when the oxyalkylated polyol and monohydric surface active agent are phosphated together, is better than either component alone.

In the foregoing example, the phosphation was done with polyphosphoric acid, but it can be done with phosphorous pentoxide. However, the reaction is smoother with polyphosphoric acid and is much easier to control.

Examples of further oxyethylated polyhydric compounds which can be obtained by the oxyalkylation procedure of Example I and can be phosphated as therein described are as follows:

TABLE 1.OXYALKYLATED COMPO UNDS Polyhydric Compound Ethylene oxide, Name Percent Percent Example:

A1 Glvcerine (Ex. 1) 50. 0 50. 0 do 25. 8 74. 2 7. 7 92. 3 25. 0 25. 0 50. 0 49. 3 50. 7 35. 0 65. 0 84 16. 0 58. 7 41. 3 31. 2 G8. 8 18. 6 81. 4 70. 5 29. 5 50. 0 50. 0

Surface Active Agent Ethylene oxide, Name Percent Percent Example:

B Nonyl phenol 56. 6 44. 4 B do 40.0 60 B 32.5 67.5 BL"- ..do 28. 9 71.1 13 Tridecyl alcohol 30. 7 69. 3 3a.. .dO 47. 5 52. 5 13 Higher alcohols (butanol bottoms) 53. 3 46. 7 B 41.2 58. 7

..... 6-10 Carbon normal alcohols (Altol 610) V 1 Catalyst-B F, etherate complex.

1 Solvent, dioxane. Plus 0.1% caustic potash;

TABLE 2 Parts Parts-Oxypoly- Parts After treatment parts alkylated phosorganic Time, Ten-113., Ex. compounds phoric solvent 111'. C H2O Caustic Alkanol 2 {iggfgg 125 1 100110 405 03 0 3 100A1;100B2 200 50 0.5 90-95 400 0 0 100A1; 50132 200 30 0.5 90-95 350 0 0 100.51; 50134 200 30 0.5 90-95 350 0 0 100A1; 5032 300 30 0.5 90-95 450 0 0 100A1 ;50B3 300 30 0.5 90-95 450 0 0 s {18813: gggi} 300 30 0. 5 90-95 450 0 0 9 100m; 3013 200 20 0.5 90-95 330 0 0 1002. 2013 200 20 0.5 90-95 320 0 0 100A1;10B1 200 10 0.5 90-95 310 0 0 100.51; 5013 200 1 30 0.5 9095 40 z 0 50A1;100B4 125 0 0.5 90-95 275 0 0 50A 100134 50 0 0.5 90-95 200 0 0 20112100134 100 0.5 90-05 220 0 0 100m; 4013 200 30 0.5 90-95 340 0 0 100A1;100Bg 400 30 0.5 90-95 340 0 0 100A1;100BB 400 30 0.5 90-95 000 0 125 100155; 5013 200 30 0.5 90-95 350 0 0 20 100A 50133 200 38} 0.5 90-95 350 0 0 21 100m; 50133 200 30 0.5 90-95 350 0 0 75m; 75138 200 0 0.5 90-95 350 0 0 7511075135 200 30 0. 5 90-95 350 0 0 100m; 50133 150 4 50 0. 5 90-95 350 0 0 100G; 50B; 200 0 0. 5 90-95 350 0 0 100A1; 75B5 200 1 30 0. 5 90-95 375 0 0 100m; 10033 200 30 0. 5 90-95 400 0 0 75m; 75B3 200 30 0. 5 90-95 350 0 0 75A 10013 200 30 0. 5 90-95 375 0 0 50m; 10013 200 30 0. 5 90-95 350 0 0 25A1; 100B; 200 0. 5 90-95 325 0 0 100113; 100134 150 0 0. 5 90-95 200 0 0 100A;; 10013 150 0 0. 5 90-95 200 0 0 1O0A3;100B3 250 1 30 0.5 90-95 450 0 0 6OA1; 21535 170 0 0.5 100 395 0 50 50A; 215135 255 0 0.5 100 430 0 50 00m; 21513 340 0 0.5 100 565 0 0 301 .1; 215135 170 0 0. 5 100 305 0 50 30m; 215135 255 0 0.5 100 450 0 50 30m; 215135 340 0 0.5 100 535 0 50 120111; 215135 170 0 0.5 100 455 0 50 12015 215513 255 0 0.5 100 540 0 50 120m; 215B@ 340 0 0. 5 100 025 0 50 120m; 21513 425 0 0. 5 100 710 0 50 50m; 215135 340 0 0. 5 100 505 0 50 30m; 2153a 170 0 0. 5 100 365 0 50 9015 32013 340 0 0. 5-1 100 700 0 50 4s A1;l60B5 340 0 0. 5-1 100 495 0 5 0 5 0 49 120A 215135 425 0 1 90 1,060 0 50 1 99% isopropanol. 5 n-Propanol 2 Liquid 58% NgOH in water. a Methanol.

Example 50 4; 345 parts by weight of ethylene oxide per 130 parts of the This example illustrates carrying out the process by heavydalcctihol. g W3 by y of finely adding the oxyalkylated polyol and oxyalkylated surface groun PO f a as t e alka me catalyst The active agent to warmliquid pols/phosphoric acid ethylene ox1de add1t1on took about one hour at 120- 425 parts of polyphosphoric acid was placed in a three 9 3 Was followed by a one hour recycle Period neck reaction flask provided with agitation and heating 50 means. The temperature was raised to 70 C. and a mix- Example 51 Illustrates the use of P205 as the P P ture of the following, heated to 50 C., was slowly added: mg agent 215 parts B 120* part A Lower alkanols, part1cularly n-propanol or isopropanol,

The addition rate was regulated so that the temperature may be present the Phosphatlhg reaehoh as vleeoslty of the reaction mass increased to 130 C. When the addi- 55 g agentsi other i' z i f be used edloxahe tion was finished, the reaction mass was held at 130 C. an to e Ower a ano P osphates whlch form by for 30 minutes. It was then cooled to 85 C., 50 parts of the reaehoh of the fhkahol f e 'lf e agent are n-propanol was added, followed by cooling to C., the hot Parheulafly aehve as scale lhhlbltorsaddition of 50 parts methanol, agitation for 10 minutes Oh the other hahdqphosphated esters 'f Salts there and the addition of 0 parts Water 50 of of oxyethylated higher alkanols having at least 4 car- EX m 16 51 bons, preferably 6 to 20 carbon atoms, are used in the a p invention in admixture with, or as mixed esters with, the

III a reaction Vessel q pp With a Surfer, 100 Parts phosphated esters of oxyalkylated polyols. The oxyethyl- 0f the Oxyalkylated glyceflne 1 Parts of oxyethylated ated alkanols contain about 220 mols of oxyethylene hlgh bolllng alcohols and Parts 2 5 are heated groups per mol of alkanol and have the general formula and reacted at 185-190 C. The reactlon mlxture is refluxed for 15 minutes. After cooling, the reaction pro- 2 2 )2-20 arts of w te and is neu- 28 2 222 a I wherein R 1s a straight chain or branch chain alkyl group The Specific mixture in this example was a heavy y of at least 4 and preferably at least 6 carbons. Mixtures hol mixture called butanol bottoms and comprised nof two or more alkanols are also confemplated by the butano], 3%; c5 alcohols, C6 alcohols, c 1nvent1on. Other higher molecular weight oxyalkylated alcohols, C8 alcohols, 45%; d C e l h l surface active substances containmg prlmary hydroxyl 14%. The alcohols were mostly primary, branch chain g p Whlch can be Phosphated Wlth P yp p alkanols. They were oxyethylated at 120160 C. with acid or P 0 e.g., the oxyethylated alkyl phenols, provide compositions in the form of mixed phosphate esters or mixtures of esters which are very useful.

In preparing these compositions, the weight ratio of oxyalkylated polyol to oxyalkylated monohydric surfactant containing a Z-hydroxyethyl group is preferably within the range of 1:10 to 10:1.

The compositions of the invention are especially effective in the inhibition of scaling on metal surfaces by calcium sulfate, barium sulfate, and calcium carbonate. They are useful in the oil production industry to prevent deposits of these scale-producing compounds on metal surfaces of pumps, pipes, valves, tanks, and the like when waters containing the scale-producing compounds (or precursors thereof, e.g., calcium bicarbonate) are treated in the concentrations aforesaid, i.e., 0.5 to 100 parts per million. Places where scale build up is most likely to become troublesome are those in the liquid handling systems wherein there is a change in fluid pressure, a change in fluid temperature, or a change in fluid flow rate.

The invention may be used in waterflood systems used to inject water into subterranean formations, wherein the water is brackish or is a brine conducive to scale formation on metal surfaces of the waterflood system. Typical brines encountered in waterflood operations, wherein water is drawn from sources available at or near the waterflood site, are:

Brine A Brine B Any of the products previously descrbied can be used to prevent scale formation on metal Walls of pipes, pumping equipment and storage tanks used to inject flood waters into subterranean formations. The dosage will vary depending on the particular composition and the type of brine in the formation but, in general, effective control is obtained with 10 to 20 parts per million (p.p.m.) of inhibitor and in some cases as low as 0.5 p.p.m. is effective. Thus, the inhibitor of Example 49 is effective in inhibiting scale by brines A and B at 10-20 p.p.m.

In cooling waters of closed cooling systems, wherein the cooling water is a typical municipal tap water, maintenance of dosage levels of -30 p.p.m. are typical, although higher levels up to about 100 p.p.m. may be needed or desired in particular cases.

In low pressure boilers, dosage levels in the range of 50-250 p.p.m. may be employed in the feed water, a typical level being about 80-100 p.p.m.

The compositions of the invention are useful in a number of areas where scaling of metal surfaces, particularly ferrous metal surfaces, by barium sulfate, calcium sulfate and/or calcium carbonate is a problem. By control of scale formation, breakdowns, maintenance, cleaning and repairs caused or necessitated by scale formations can be minimized.

In comparative tests using brines made by dissolving 7.5 grams of sodium chloride and 8.33 grams of calcium chloride in distilled water sufficient to make 1 liter (Brine C) and 7.5 grams sodium chloride plus 10.66 grams Na SO in distilled water sufficient to make 1 liter (Brine D), it was found that the composition of Example 1 was partially effective in preventing calcium sulfate deposition at 1 p.p.m. and completely effective at 2 p.p.m. when 50 ml. of each brine were mixed and heated for hrs., at 160 F. A control test with no additive gave a deposit of 1350 p.p.m. CaSO calculated as CaCO The composition of Example 44 gave no deposits at 1 p.p.m. added to 100 ml. of the brines C and D. At the same dosage a phosphated OXyethylated g ycerine without the oxyethylated tridecyl alcohol component gave a deposit of 400 p.p.m. CaSO calculated as CaCO thereby indicating that the mixed ester is more effective than the phosphated oxyethylated polyol alone.

Calcium carbonate deposition tests also indicated a superiority for the compositions of the invention. Thus, the compositions of Examples 44, 47 and 48 prevented calcium carbonate deposition on the surface of test cells containing 20 ml. of brine (Brine E) made by dissolving 8.4 grams of NaHCO in one liter of distilled water, ml. of brine (Brine F) made by dissolving 11.1 grams of CaCl in 1 liter of distilled water and 90 ml. of brine (Brine G) which was a 10% solution of sodium chloride in water, mixed together and heated for 20 hours at F. Complete inhibition of calcium carbonate deposition was obtained with all three compositions at dosages of 5 p.p.m., 10 p.p.m. and 30 p.p.m. and with Example 44 at 3 p.p.m. The blank control deposited 380 p.p.m. A phosphated polyol was completely effective at a dosage of 10 p.p.m. and 30 p.p.m. but only partially effective at 3 p.p.m. and 5 p.p.m.

The process of the invention can be carried out with relative ease and is especially important where the polyols have closely spaced hydroxyls such as glycerine and pentaerythritol. The addition of 2-hydroxyethyl groups spaces the hydroxyl groups and makes it easier to produce phosphate esters without forming a viscous mass. The final products are preferably acidic, e.g., pH 4.5-6, because water solubility decreases and solids precipitate at pl-ls above 7.

In the process for making phosphate esters previously described it will be understood that where a solvent is used the process is carried out at a temperature below the boiling point of the solvent.

The solvents used act as combination solvents and viscosity control agents, although any solvents, e.g. hydroxyacetic acid, having a reactive hydroxyl group will react in the phosphation and influence the overall composition of the final product.

It will also be understood that other surface active agents can be used provided they contain a 2-hydroxyethyl group. Numerous examples are given in McCutcheons Detergents and Emulsifiers 1966 Annual.

In a number of oil fields in West Texas and other areas, water floods have been established in which waters incompatible with the connate waters were used for injection. This occurs when a good source of compatible water is not available. Most of these floods are using a high sulfate water to flood a formation which has a high calcium content water. As the waters reach the producing well they mix, and a calcium sulfate deposition oc curs, either in the formation at the well bore or in the producing equipment. This requires the removal of the tubing, rods and pump for cleaning, and a fracturing job if the formation is plugged, which is the case most of the time. By the practice of the present invention the formation of scale in the producing equipment and underground formation can be reduced or prevented. However, as the scale forms in the producing formation, the scale control chemical must be squeezed into the producing underground formation so it can be produced back slowly in one of the waters before they mix. To give long term scale inhibition the chemical must be adsorbed on the underground formation in such a manner that it is slowly released into the water as it passes over the formation so that a chemical concentration of one to 10,000 ppm. is always in the water. Some scale control compounds when squeezed into the formation are so tightly adsorbed that little, if any, feedback occurs, while others are essentially not adsorbed and feedback occurs immediately with no extended protection given. The chemicals of the present invention have unique adsorption-desorption properties in that they are adsorbed on solid surfaces and slowly released into the produced water or brine over a period of time to give long term protection against scale deposition in the surfaces of the formation face and the producing equipment.

In a typical application, five to ten barrels of water from a producing oil well are pumped into an oil well. A chemical composition as herein described is then injected into the well and displaced or squeezed through the underground oil-bearing formation by pumping 50 to 150 barrels of produced water into the well, depending upon the amount of water being produced. The produced oil and water are then pumped from the Well.

Similarly, the invention is applicable to the treatment of water supply wells. The pro-addition of Water to the well can be omitted. The phosphate mixed esters or mixture of esters can also be added directly to the input well of a waterfiood system consisting of one or more input wells and one or more producing wells.

The invention is hereby claimed as follows:

1. A process for preventing scale deposits of at least one of barium sulfate, calcium sulfate, and calcium carbonate on solid surfaces in contact with water containing said scale-forming chemicals which comprises contacting said solid surfaces with said water while maintaining therein an effective scale inhibiting amount of a phosphated mixed ester, or mixture of phosphated esters of (A) a polyol of the formula wherein R is a saturated, hydrocarbon radical having 2-6 carbon atoms, R is a member selected from the group consisting of CH CH and x is a number average in the range of -5, inclusive, y is a number average in the range of 1-6, inclusive, and the sum of x plus y equals 2-6, and z is a number average in the range of 0-30, inclusive, and (B) a monohydric oxyalkylated surface active agent having a Z-hydroxyethyl group, said surface active agent being oxyalkylated with two to twenty moles of ethylene oxide per mole thereof and selected from the group consisting of alkyl phenols containing 4-12 carbon atoms in the alkyl grouping, mixtures thereof and oxyethylated higher alkanols having 4-20 carbon atoms in the alkyl portion thereof, said phosphated mixed ester having an average of at least one and up to all of the hydroxyls of the 2-hydroxy ethyl groups and on an average of zero up to substantially all of the hydroxyl groups directly attached to the radical R replaced by phosphate ester groups, said phosphate ester groups consisting essentially of one or both of a member selected from the group consisting of with the further proviso that the ratio of (A) to (B) is within the range of 1:10 to :1.

2. A process as claimed in claim 1 wherein said amount is 0.5 to 100 parts per million parts of said water.

3. A process as claimed in claim 1 in which said ester, or esters, is at least partially in the form of a salt thereof from the class consisting of alkali metal, ammonium, and water soluble amine salts.

4. A process as claimed in claim 1 wherein said hard water is a natural water or brine.

5. A process as claimed in claim 1 wherein said polyol is derived by oxyethylation of glycerol with 1.5 to 2.5 mols of ethylene oxide per mol of glycerol.

6. A process as claimed in claim 1 wherein said surface active agent is an oxyethylated alkyl phenol containing 4-12 carbon atoms in an alkyl group derived by oxyethylation with about 2-20 mols of ethylene oxide per mol of said alkyl phenol.

7. A process as claimed in claim 1 wherein said surface active agent is oxyethylated tridecyl alcohol containing 2 to 20 moles of ethylene oxide per mole of alcohol.

8. A process as claimed in claim 1 wherein said surface active agent is an oxyethylated mixture of 6-l0 carbon atom primary alcohols containing 2 to 20 moles of ethylene oxide per mole of alcohol.

9. A composition which is a phosphated mixed ester or mixture of phosphated esters of: (A) a polyol of the formula wherein R is a saturated, hydrocarbon radical having 2-6 carbon atoms, R is a member selected from the group consisting of CH CH and CH2CH x is a number average in the range of 0-5, inclusive, y is a number average in the range of l6, inclusive, and the sum of x plus y equals 2-6, and z is a number average in the range of 0-30, inclusive, and (B) a monohydric oxyalkylated surface active agent having a 2-hydroxyethyl group, said surface active agent being oxyalkylated with two to twenty moles of ethylene oxide per mole thereof and selected from the group consisting of alkyl phenols containing 4-12 carbon atoms in the alkyl grouping, mixtures thereof and oxyethylated higher alkanols having 4-20 carbon atoms in the alkyl portion thereof, said phosphated mixed ester having an average of at least one and up to all of the hydroxyls of the 2-hydroxy ethyl groups and on an average of zero up to substantially all of the hydroxyl groups directly attached to the radical R replaced by phosphate ester groups, said phosphate ester groups consisting essentially of one or both of a member selected from the group consisting of o -Oi -OH and -o-i -0- with the further proviso that the ratio of (A) to (B) is within the range of 1:10 to 10:1, and that said composition is obtained by phosphating (A) and (B) with a compound from the group consisting of liquid polyphosphoric acid and phosphorus pentoxide at a temperature of 50 C. to C.

10. A composition as claimed in claim 9 in which the salts are alkali metal salts of said esters.

11. A process as claimed in claim 1 in which said mixed phosphated ester or mixture of esters is injected into a well and displaced into underground formation where the mixed phosphated ester or mixture of esters is adsorbed on the surfaces of the formation to be slowly released into the produced water or brine over a period of time to give long term protection against scale deposition on the surfaces of the formation face and the producing equipment.

12. A process as claimed in claim 11 in which said esters comprise as one of the esterifying groups oxyethylated glycerine containing 1.5 to 2.5 moles of ethylene oxide per mole of glycerine and as another esterifying group oxyethylated nonylphenol containing 4 to 14 moles of ethylene oxide per mole of nonylphenol.

13. A process as claimed in claim 11 in which said esters comprise as one of the esterifying groups oxyethylated glycerine containing 1.5 to 2.5 moles of ethylene oxide per mole of glycerine and as another esterifying group oxyethylated tridecyl alcohol containing 4 to 14 moles of ethylene oxide per mole of alcohol.

14. A process as claimed in claim 1 in which said mixed phosphated ester or mixture of esters is added to water used for cooling.

1 1 1 2 15. A process as claimed in claim 1 in which said 3,309,427 3/1967 Zech et a1 260-929 mixed phosphated ester or mixture of esters is added to 3,346,670 10/1967 Papalos 260-951 boiler feed water.

LEON D. ROSDOL, Primary Examiner References (Med 5 W. SCHULZ, Assistant Examiner UNITED STATES PATENTS 3,004,056 10/1961 Hunn et a1 260-929 3,263,003 7/1966 Friedman 260-951 210-58; 252-855, 89

3,275,667 9/1966 Bohunek 260-929 mg UNITED STATES PATENT OFFICE CERTIFICATE F QQRRECTION Patent No. 5 ,502,58'T Dated March 2 1970 Inventor(s) James R. Stanford et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 5, line 11, "In organic" should read Inorganic Column 4, line 8, "56.6%" should read 55.6% in Table 1, section B, entry B "56.6%" should read 55.6%

Column 5, table 2, under "Parts organic solvent", entries %,5, 6,7,8,17,18,l9,27,28,29,30, and 31, in each entry, "30" should read 50 in entry 10, "20" should read 2O in entry 37, under "Alkanol", "0" should read 5O (SEAL) Anew Edward MFIetcherJm WILLIAM E. sum, A i ()ffi Comi ssioner of Patents P0405" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,502,587 Dated March 24, 1.270

Inventor(s) James R. Stanford et al It: is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, line 11, "In organic" should read Inorganic Column 4, line 8, "56.6%" should read 55.6% in Table 1, section B, entry 13;, "56.6%" should read 55.6%

Column 5, table 2, under "Parts organic solvent", entries 4,5, 6,7,8,l7 l8,l9,27,28,29,30, and 51, in each entry, "30" should read 30 in entry 10, "20" should read 2O in entry 37, under "Alkanol", "0'' should read 5O SIWWQ A? SEALED SEP 15% (SEAL) Atteat:

Edward MFlelcherJtwmm r. sum, JR. Anesting Officer Gomisaioner of Patents 

